Methods to make nanolaminate thermal barrier coatings

ABSTRACT

Methods and apparatus to make multilayer thermal barrier coatings for superalloy substrates such as turbine blades or vanes are disclosed. The methods produce non-homogeneous, nanometer-size, successive layers and a non-homogeneous interfacial layer without the use of baffles. Methods are also disclosed to use a lower cost metallic source and an oxygen bleed to create alumina or tantalum oxide vapor, to use a tantalum oxide or an alumina ingot and a low pressure inert gas feed to direct the vapor clouds, to use pulsed evaporation from a secondary vapor source to create non-homogeneous multilayer coating on non-rotated substrates, to use an electric bias to direct the vapor clouds, and to use a mechanical system to direct the vapor clouds or move and position the article to be coated in the clouds.

GOVERNMENT RIGHTS

[0001] This invention was made with Government support under Contract No. N00421-01-0019 awarded by the United States Navy. The Government has certain rights in this invention.

BACKGROUND OF THE INVENTION

[0002] The present invention generally relates to apparatus and methods for forming nanolaminate thermal barrier coatings for turbine engine blades and vanes and more specifically to apparatus and methods for forming thermal barrier coatings composed of a series of non-homogeneous nanometer—to micron-sized layers for turbine blades or vanes.

[0003] Increased gas turbine engine operating temperatures often result from efforts to improve on overall engine efficiency as well as to reduce emission of contaminants released to atmosphere. Increased operating temperatures, however, result in concerns over the ability of various engine components, such as turbine blades and vanes, to remain durable and maintain their mechanical strength. These concerns have been addressed in the following two principal ways: first, the formulation of superalloys, such as nickel and cobalt based, having high temperature capabilities; and, second, the application of protective thermal barrier coatings (TBC's) which insulate the components thus minimizing their service temperatures.

[0004] Referring to the application of protective coatings, it is known that the characteristics of TBC's must include the capability to strongly adhere and remain adhered to the component to which it is applied, and low thermal conductivity. Typically, TBC's applied to superalloy substrates have included a bond coat and a ceramic top layer, the latter being applied either by the process of plasma spraying or by the process of electron beam physical vapor deposition (EB-PVD). Use of the EB-PVD process results in the outer ceramic layer having a columnar grained microstructure. Gaps between the individual columns allow the columnar grains to expand and contract without developing stresses that could cause spalling. Prior art has disclosed thermal barrier coatings for superalloy substrates that contain a MCrAlY layer, an alumina layer, and an outer columnar grained ceramic layer. Also TBC's for superalloy substrates have included those that contain an aluminide layer, an alumina layer, and an outer columnar grained ceramic layer with the ceramic layer commonly being zirconia stabilized with yttria.

[0005] U.S. Pat. No. 4,676,994 to Demaray discloses that a layer of dense stabilized zirconia can be deposited onto the bond coating when the gas pressure within the chamber is less than 0.0001 torr. Subsequent injection of oxygen at a pressure of 0.0001 to 0.01 torr into a stabilized zirconia vapor cloud increases the oxygen content of the ceramic layer and initiates growth of substantially stoichiometric columnar ceramic grains with intercolumnar porosity for strain tolerance. Tubes and nozzles are used to direct the oxygen gas to impinge upon the substrate.

[0006] U.S. Pat. No. 5,534,314 to Wadley et al. discloses the use of a carrier gas to entrain the evaporant in the carrier gas stream and coating the part with the carrier gas stream containing the entrained evaporant. Depending upon the requirements of the coating, the carrier gas may be oxygen, nitrogen, helium or another inert gas such as, methane or acetylene. The carrier gas is used to increase the deposition rate onto the substrate and, because gas is used with associated pressure (0.001 torr to 1 atmosphere), the coating is more uniform on complex shaped parts and less line of sight limited. The process disclosed by Wadley does not deal with nanolaminates.

[0007] U.S. Pat. No. 6,054,184 to Bruce et al. discloses a method and apparatus for forming a multilayer thermal barrier coating such that the coating is composed of substantially homogeneous layers of different materials. The process requires two ceramic vapor sources separated by a baffle to make multi-layer TBC's composed of homogeneous successive layers of stabilized zirconia+alumina. The use of a baffle significantly reduces the efficiency of deposition, as much of the vapor cloud is wastefully deposited on the baffle.

[0008] U.S. patent application Ser. No. 09/535,394, filed Mar. 24, 2000, which Applicant hereby incorporates herein by reference, filed on behalf of the assignor herein, discloses a thermal barrier coating which includes a columnar grained ceramic layer applied to an aluminide or MCrAlY bond coat by EB-PVD. The ceramic layer is comprised of a plurality of layers of zirconia stabilized with 20 percent yttria and the interfaces between the layers are decorated with particles selected from a group consisting of Ta₂O₅ and alumina. A baffle is not required but is optional in the disclosed process which is aimed at producing a lower conductivity thermal barrier coating.

[0009] Although prior art has resulted in various improved methods and apparatus for thermal barrier coatings, none results in columnar grained thermal barrier coatings composed of a multitude of non-homogeneous, nanometer—to micron size, successive layers separated by non-homogeneous interfaces stabilized by nanometer-sized second phase particles.

[0010] As can be seen, there is a need for an improved apparatus and method for forming non-homogeneous nanometer—to micron-sized multi-layer thermal barrier coatings for superalloy substrates such as turbine blades or vanes.

SUMMARY OF THE INVENTION

[0011] In one aspect of the present invention, a thermal barrier coating deposition apparatus is disclosed. It comprises: a vacuum chamber; a primary crucible and an offset secondary crucible placed within the vacuum chamber; a ceramic material within the primary crucible; a metallic or ceramic material placed within the secondary crucible; two electron beam guns within the vacuum chamber each producing electron beams aimed, one toward the ceramic material within the primary crucible and another toward the metallic or ceramic material within the secondary crucible; articles on a rotary holder placed internally within the vacuum chamber; the rotary holder being positioned within the chamber such that the angle formed by the article holder's rotation axis and the center of the evaporation surface of the materials within the primary and secondary crucibles is 20 degrees or greater; oxygen bleed supply tubes protruding into the vacuum chamber aimed in the direction of the vapor cloud and the articles; whereby upon actuation of the electron beam guns and release of the oxygen gas, ceramic and/or oxidized metallic vapor clouds together with rotation of the articles within the vapor clouds coats the articles with a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous, nanometer—to micron thickness layers of ceramic material which have dispersed molecules of the oxidized secondary material, with a multiphase interfacial layer containing primary and secondary oxides separating each. The primary layer thickness and interface layer composition are established by controlling the electron beam power applied to the evaporation sources and the rate of specimen rotation.

[0012] In another aspect of the present invention, there is disclosed an apparatus comprising: a vacuum chamber; a primary crucible containing ceramic materials and a secondary crucible containing metallic or ceramic materials; a plurality of electron beam guns emitting electron beams aimed at the material within the crucibles; articles to be thermal barrier coated placed on a holder internally within the vacuum chamber; a plurality of tubes protruding into the vacuum chamber supplying oxygen gas to the articles; whereby upon actuation of the electron beam guns and release of the oxygen gas, ceramic and oxidized metallic vapor clouds are produced from the crucibles coating the articles with a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous nanometer—to micron-thickness layers of the primary ceramic material which have dispersed molecules of the oxidized secondary material, with a multiphase interfacial layer, consisting of finely dispersed particles of oxidized secondary material and the primary ceramic material separating each.

[0013] In yet another aspect of the present invention, a method of depositing a thermal barrier coating on articles is disclosed. The method comprises the steps of: positioning one or more articles, such as turbine blades or vanes, within the mixing zone of a primary ceramic vapor cloud and a secondary metallic vapor cloud; simultaneously heating and melting a portion of each of the ceramic and metallic materials to produce vapor clouds; adding oxygen to convert metallic vapor to an oxide vapor; apportioning power from an electron beam to the ceramic and metallic sources; rotating the articles within the combined vapor clouds such that the mixed vapors may deposit a multilayer thermal barrier coating; controlling the rates of coating deposition such that the multilayer zone within the thermal barrier coating has a minimum of one interfacial layer per micron of coating thickness.

[0014] In yet one final aspect of the present invention, a method of thermal barrier coating is disclosed, said method comprising the steps of: positioning one or more articles within the mixing zone of the primary ceramic vapor cloud and the secondary ceramic or oxidized metallic vapor cloud; simultaneously heating and melting a portion of each of said ceramic and metallic materials to produce vapor clouds and adding oxygen gas; apportioning power from electron beams such that the majority of the deposited vapor is derived from the primary ceramic source; pulsing power to enable deposition of a multilayer thermal barrier coating and a multiphase interfacial layer separating each of the primary material layers.

[0015] These and other features, aspects and advantages of the present invention will become better understood with reference to the following drawings, description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016]FIG. 1 is a schematic elevational view of a dual source electron beam physical vapor deposition process apparatus according to an embodiment of the present invention;

[0017]FIG. 2 is a schematic elevational view of a dual source, single electron beam physical vapor deposition process apparatus according to another embodiment of the present invention;

[0018]FIG. 3 is a schematic elevational view of a pulse source, dual electron beam physical vapor deposition process apparatus according to another embodiment of the present invention;

[0019]FIG. 4 is a schematic elevational view of a dual source electron beam physical vapor deposition process apparatus involving ionization of the evaporated vapor according to another embodiment of the present invention; and

[0020]FIG. 5 is a schematic elevational view of a dual source electron beam physical vapor deposition process apparatus according to yet another embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0021] The following detailed description is of the best currently contemplated modes of carrying out the invention. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims.

[0022] The present invention generally provides methods to make multiple layer thermal barrier coatings for superalloy substrates such as turbine blades or vanes, without use of a baffle. The process results in a thermal barrier coating composed of non-homogeneous nanometer—to micron-size layers separated by a non-homogeneous interfacial layer composed of secondary and primary ceramic oxides.

[0023] Methods are also disclosed to use a lower-cost metallic source and an oxygen bleed to create alumina or tantalum oxide vapor, to use a tantalum oxide or an alumina ingot and a low pressure oxygen or inert gas bleed to direct the ceramic or oxidized metallic vapor cloud produced by the secondary evaporation source, to use pulsed evaporation from a secondary vapor source to create non-homogeneous multilayer coating on non-rotated substrates, to ionize the vapor and use an electric bias on the component to attract the vapor and produce dense layers within the coating, and to use a mechanical system to cyclically position the article to be coated in the primary and secondary vapor clouds. This is unlike prior art whereby two ceramic vapor sources separated by a baffle are needed to make multilayer thermal barrier coatings composed of homogeneous successive layers of stabilized zirconia+alumina.

[0024] Referring to the accompanying drawings (in which like reference numerals indicate like parts throughout several views), and in particular to FIG. 1, there is shown a schematic elevational view of a dual source EB-PVD process apparatus 10 according to an embodiment of the present invention. The deposition process apparatus 10 may be comprised of a vacuum chamber 12 internal to which may be placed a primary crucible 14 and a secondary crucible 16. Primary crucible 14 may contain a ceramic material such as a stabilized zirconia ingot 18 whereas the secondary crucible 16 may contain a metallic or ceramic material, such as an Al₂O₃, Al, Ta₂O₅ or Ta ingot 20. Protruding into the vacuum chamber 12 may be two electron beam guns 22 of a configuration well known in the art. Said electron beam guns may be arranged such that corresponding electron beams 24 are aimed, one to the upper surface of the coating material within said primary crucible 14, and the other to the upper surface of the coating material within the secondary crucible 16. Articles 26, such as turbine blades, vanes, or other similar components, may be placed on a rotary holder 28 which may rotate in a direction such as shown by arrow 29. The rotary holder 28 may be positioned within the vacuum chamber 12 such that the angle formed by the article 26 holder's rotation axis and the center of the evaporation surface of the materials within the primary 14 and secondary 16 crucibles may be 20 degrees or greater. Two oxygen bleed 30 supply tubes may be placed on the sides of vacuum chamber 12 such that a measured supply of oxygen may be aimed in the direction of articles 26. Upon actuation of the electron beam guns a ceramic vapor cloud 34 and an oxidized metallic or ceramic vapor cloud 36 may be produced.

[0025] The dual source EB-PVD process, using the apparatus depicted in FIG. 1, involves the following steps:

[0026] 1. Positioning one or more articles 26 within the mixing zone 32 of the primary ceramic vapor cloud 34 and the secondary ceramic or oxidized metallic vapor cloud 36 produced by separate vapor sources. The primary source may be a ceramic material, such as a stabilized zirconia ingot 18, and the second source may be a ceramic or metallic material, such as an Al₂O₃, Al, Ta₂O₅, or Ta ingot 20.

[0027] 2. Simultaneously heat, melt, and evaporate a portion of each of the ceramic and metallic materials to produce a primary ceramic vapor cloud 34 and a secondary ceramic or oxidized metallic vapor cloud 36 that coexist within vacuum chamber 12. Oxygen may be added to the chamber through oxygen bleed 30 supply tubes to convert metallic vapor to an oxide vapor and direct it toward the articles on the rotating holder 28. The pressure of the oxygen in the chamber may be in the range of 0.0001 to 0.01 torr during coating deposition.

[0028] 3. Power from electron beam 24 may be apportioned to the primary and secondary sources; at least 85% of the vapor that deposits onto the article 26 will be derived from the primary ceramic source; at least 1% of the vapor that deposits onto the article 26 may be derived from the secondary metallic or ceramic source.

[0029] 4. Rotate the article 26 within the combined vapor clouds 34 and 36 such that the mixed vapors may deposit a multilayer TBC composed of an alternating sequence of non-homogeneous layers; layers may be composed of the primary ceramic material which may have dispersed oxide molecules or particles of the second material; a interfacial layer composed of secondary and primary phase particles may separate each of the primary ceramic layers; interfacial layers may consist of a mixture of finely dispersed, nanometer—sized particles of the secondary ceramic or oxidized metallic material, the primary ceramic material, and nanometer-size porosity.

[0030] 5. Controlling the rates of coating deposition and article 26 rotation rates such that the multilayer zone within the TBC may have a minimum of one interfacial layer per micron of coating thickness.

[0031] 6. Thermal radiation from the evaporating ingot sources and electrical resistance heaters (not shown) may maintain article surfaces at temperatures within the 950° to 1150° C. range during coating deposition, with temperatures in the 1000° to 1100° C. range being preferred.

[0032] Referring now to FIG. 2, there is shown a schematic elevational view of a dual source, single-gun EB-PVD process apparatus according to another embodiment of the present invention. Said deposition process apparatus 10 is comprised of essentially the same elements as the apparatus depicted in FIG. 1, and includes a vacuum chamber 12, a primary crucible 14, a secondary crucible 16, correspondingly containing ceramic and metallic material, articles 26 positioned on a rotating holder 28, and oxygen bleed 30 supply tubes. However, the electron beams 24 may be provided by a single electron beam gun 38, from which power is apportioned between the two vapor sources. The electron beams 24 may jump rapidly between the ingot sources (up to several hundred times per second) to achieve continuous rates of evaporation during the multilayer TBC deposition process, which, in all other respects, is the same as described above for the apparatus of FIG. 1.

[0033] Other alternate embodiments, applicable to the EB-PVD process apparatus of FIGS. 1 and 2 may involve substituting the metallic, Al or Ta ingot 20, with an oxide ingot (e.g., alumina or tantalum oxide). Also a further variation may be the use of a low pressure inert gas, such as argon, to replace the oxygen being introduced through the oxygen bleed 30 supply tubes, and direct the vapor cloud from the Al or Ta ingot 20. Oxygen may still be bled into the system using other inlets or with the inert gas.

[0034] Referring now to FIG. 3 there is shown a schematic elevational view of a pulse source, dual electron beam gun EB-PVD process apparatus according to yet another embodiment of the present invention. The deposition process apparatus 10 may be comprised of a vacuum chamber 12 internal to which may be placed a primary crucible 14 and a secondary crucible 16. Primary crucible 14 may contain a ceramic material such as a stabilized zirconia ingot 18 whereas the secondary crucible 16 may contain a ceramic or metallic material, such as an Al₂O₃, Al, Ta₂O₅, or Ta ingot 20. Protruding into to the vacuum chamber 12 may be two electron beam guns 22 of a configuration well known in the art. Said electron beam guns may be arranged such that corresponding electron beams 24 are aimed, one to the upper surface of the ceramic material within said primary crucible 14, and the other to the upper surface of the ceramic or metallic material within the secondary crucible 16. Articles 26, such as turbine shrouds (blade outer air seals) or combustion components, may be placed on a non-rotating holder 40. Oscillation of the holder about its axis is permitted but not required. Two oxygen bleed 30 supply tubes may be placed on the sides of vacuum chamber 12 such that a measured supply of oxygen may be aimed in the direction of articles 26. Upon actuation of the electron beam guns a ceramic vapor cloud 34 and a ceramic or oxidized metallic vapor cloud 36 may be produced. Power to the electron beam gun 22 directed at the material within the secondary crucible 16 may be periodically pulsed to change the evaporation rate so that the deposition rate of material from the secondary ingot increases from less than 1% to a maximum of 50% of the rate of deposition of the material evaporated from the primary ceramic stabilized zirconia ingot.

[0035] The pulsed source EB-PVD process using the apparatus depicted in FIG. 3, involves the following steps:

[0036] 1. Positioning one or more articles 26 within the mixing zone 32 of the primary ceramic vapor cloud 34 and the secondary ceramic or oxidized metallic vapor cloud 36 produced by separate evaporation sources. The primary source may be a ceramic material, such as a stabilized zirconia ingot 18, and the second source may be a ceramic or metallic material, such as Al₂O₃, Al, Ta₂O₅ or Ta ingot 20.

[0037] 2. Simultaneously heat and melt a portion of each of the primary ceramic and secondary ceramic or metallic materials to produce a ceramic vapor cloud 34 and a ceramic or metallic vapor cloud 36 that coexist within the vacuum chamber 12. Oxygen gas may be added to the chamber through oxygen bleed 30 supply tubes to convert metallic vapor to an oxide vapor and direct it toward the articles 26 on the non-rotating holder 40.

[0038] 3. Power from electron beams 24 may be apportioned between the primary and secondary sources; at least 85% of the vapor that deposits onto the article will be derived from the primary ceramic source; at least 1% of the vapor that deposits onto the article may be derived from the secondary metallic source;

[0039] 4. Power to the secondary ceramic or metallic source may be pulsed to enable deposition of a multilayer TBC composed of an alternating sequence of non-homogeneous layers; layers are composed of the primary ceramic material which may have dispersed oxide particles (molecules) of the second material; a multiphase interfacial layer separates each of the primary material layers; interfacial layers consist of a mixture of finely dispersed, nanometer—sized particles of the secondary ceramic or oxidized metallic material, the primary ceramic material, and nanometer-size porosity.

[0040] 5. Controlling the rates of pulsed deposition from the secondary such that the multilayer zone within the TBC may have a minimum of one interfacial layer per micron of coating thickness.

[0041] 6. In addition to periodically increasing and decreasing the power to the electron beams 24, pulsed evaporation from the secondary evaporation source may also be achieved by changing the raster pattern of a focused electron beam 24 from a large area to a small area or changing the power density of the electron beam 24 from a large beam (low power density) to a focused beam (high power density).

[0042] An alternate embodiment of the apparatus and described in FIG. 3 may entail substituting the metallic, Al or Ta ingot 20, with an oxide ingot (e.g., alumina or tantalum oxide).

[0043]FIG. 4 is a schematic elevational view of a dual source EB-PVD process apparatus involving ionization of the evaporated vapor according to yet another embodiment of the present invention. Said deposition process apparatus 10 is comprised of essentially the same elements as the apparatus depicted in FIG. 1, and includes a vacuum chamber 12, a primary crucible 14, a secondary crucible 16, correspondingly containing ceramic and metallic material, articles 26 positioned on a rotating holder 28, and oxygen bleed 30 supply tubes. Electron beams 24 may be provided by dual electron beam guns 22. Radio Frequency (RF) ion generators, of a configuration well known in the art, may be utilized to generate RF electrical fields 42 used to ionize the ceramic and metallic vapor clouds 34 and 36, which may then be electrically attracted to articles 26. This process may be used to alter the coating's ceramic microstructure or improve deposition efficiency. Since ionized molecules are more energetic, ionized vapor fluxes may also be used to densify (e.g., eliminate intercolumnar gaps) at the surface and/or zones within the coating. Deposited coating microstructure may be controlled by adjusting the ionization power and the electrical bias voltage applied to the articles being coated.

[0044] Yet another embodiment, shown in FIG. 5, is of a dual source EB-PVD apparatus in which a mechanical device moves articles 26 through the vapor clouds. Said deposition process apparatus 10 is comprised of essentially the same elements as the apparatus depicted in FIG. 1, and includes a vacuum chamber 12, a primary crucible 14, a secondary crucible 16, correspondingly containing ceramic and metallic material, and oxygen bleed 30 supply tubes. Electron beams 24 may be provided by dual electron beam guns 22. Articles 26 may be positioned on rotating holder 28, which may swing, by means of swing arm 44, in the direction of swing arc 46 between ceramic vapor cloud 34 and metallic vapor cloud 36. Electron beam power may be apportioned to the primary and secondary evaporation sources in such a manner that the composition of the multilayered ceramic coating contains at least 85% yttria stabilized zirconia and the amount of the secondary ceramic constituent (alumina or tantalum oxide) may be between 1 and 15%. Swing arm 44 may enter vacuum chamber 12 from the side or from the top (roof). FIG. 5 depicts one method that may be used to mechanically move the specimens in to and out of the primary and secondary vapor clouds. It will be understood that other methods are possible. For example instead of a “swinging” arm 44 as shown in FIG. 5, the arm 44 may rotate through 360°.

[0045] It should be understood, of course, that the foregoing relates to preferred embodiments of the invention and that modifications may be made without departing from the spirit and scope of the invention as set forth in the following claims. 

We claim:
 1. A thermal barrier coating deposition apparatus comprising, a vacuum chamber; a primary crucible and a secondary crucible placed internally within said vacuum chamber; a primary ceramic material placed internally within said primary crucible; a secondary ceramic or metallic material placed internally within said secondary crucible; one or more electron beam guns inside said vacuum chamber; electron beams aimed toward the upper surface of the materials within said primary and secondary crucibles; articles to be coated placed on a rotary holder within said vacuum chamber; electrical resistance and/or radiation heat sources that maintain articles within a 950° to 1150° C. range during deposition of the coating; one or more oxygen bleed supply tubes protruding into said vacuum chamber; oxygen gas, traversing through said oxygen bleed supply tubes, aimed in the direction of said articles; oxygen gas pressures in the range of 0.0001 to 0.01 torr within the chamber during deposition of the coating; whereby upon actuation of said electron beam guns and release of said oxygen gas, ceramic and oxidized metallic vapor clouds are produced from said primary and secondary crucibles coating said articles with a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous, nanometer—to micron-sized layers of ceramic material which have dispersed oxide particles (molecules) of oxidized metallic material, with a multiphase interfacial layer, consisting of finely dispersed nanometer-size particles of secondary ceramic or oxidized metallic material, the primary ceramic material, and nanometer-size porosity separating each.
 2. The thermal barrier coating deposition apparatus of claim 1, wherein said primary ceramic material is a stabilized zirconia ingot, and said secondary material is an aluminum ingot.
 3. The thermal barrier coating deposition apparatus of claim 1, wherein said primary ceramic material is a stabilized zirconia ingot, and said secondary material is an aluminum oxide ingot.
 4. The thermal barrier coating deposition apparatus of claim 2, wherein said secondary material is a tantalum ingot.
 5. The thermal barrier coating deposition apparatus of claim 2, wherein said secondary material is a tantalum oxide ingot.
 6. The thermal barrier coating deposition apparatus of claim 1, wherein the articles to be coated are turbine blades, vanes, shroud segments, or combustor components, and said rotary holder rotates said articles within said vacuum chamber.
 7. The thermal barrier coating deposition apparatus of claim 1, wherein power from said electron beams is apportioned to the primary and secondary crucibles such that at least 85% of said vapor that deposits onto said article will be derived from said primary ceramic material and at least 1% of the vapor that deposits onto said article will be derived from the ceramic or metallic material within the said secondary crucible.
 8. The thermal barrier coating deposition apparatus of claim 7, wherein power from said electron beam gun directed at the material within the said secondary crucible is periodically pulsed to change the deposition rate of the secondary oxide from less than 1% to about 1% to about 50+% of the rate of deposition of said primary stabilized zirconia ingot, and to enable deposition of a multilayer thermal barrier coating composed of an sequence of non-homogeneous layers.
 9. The thermal barrier coating deposition apparatus of claim 1, wherein the rates of coating deposition and article rotation are controlled such that the multilayer zone within the thermal barrier coating may have a minimum of one interfacial layer per micron of coating thickness, and each said interfacial layer consists of a mixture of finely dispersed particles of the secondary ceramic or oxidized metallic material and the primary ceramic material.
 10. The thermal barrier coating deposition apparatus of claim 8, wherein pulsed evaporation from said secondary crucible is achieved by changing the raster pattern of said electron beam from a large area to a small area.
 11. The thermal barrier coating deposition apparatus of claim 8, wherein pulsed evaporation from said secondary crucible is achieved by changing the power density of said electron beam from a large beam (low power density) to a focused beam (high power density).
 12. The thermal barrier coating deposition apparatus of claim 1, wherein one electron beam gun protrudes into said vacuum chamber, and the electron beam emitted from said electron beam gun jumps rapidly between the material within said primary and secondary crucible (from ten to several hundred jumps per second) to achieve continuous rates of evaporation during the multilayer thermal barrier coating deposition process.
 13. The thermal barrier coating deposition apparatus of claim 1, wherein the gas traversing through said oxygen bleed supply tubes aimed in the direction of said articles contains an inert gas such as argon.
 14. The thermal barrier coating deposition apparatus of claim 1, wherein the articles to be coated are placed on a non-rotating holder.
 15. The thermal barrier coating deposition apparatus of claim 1, wherein radio frequency (RF) generators are utilized to ionize said primary ceramic and/or secondary ceramic or metallic vapor clouds.
 16. The thermal barrier coating deposition apparatus of claim 15, wherein an electrical bias voltage is applied to the articles to attract and increase the deposition energy of the ionized coating vapor depositing onto the article.
 17. The thermal barrier coating deposition apparatus of claim 6, wherein said articles are positioned on said rotating holder, which swings, by means of a swing or rotating arm, between said primary ceramic vapor cloud and said secondary ceramic or oxidized metallic vapor cloud, and wherein said articles are moved from a stabilized zirconia vapor cloud to a secondary source vapor cloud depositing a concentration of around 1% to 20% of the alumina or tantalum oxide.
 18. The thermal barrier coating deposition apparatus of claim 1, wherein the rotary holder is situated within said vacuum chamber such that the angle formed by said holder's rotation axis and the center of the primary and secondary evaporation sources is 20 degreed or greater.
 19. An apparatus comprising, a vacuum chamber; a primary crucible containing ceramic materials and a secondary crucible containing ceramic or metallic materials; a plurality of electron beam guns emitting electron beams aimed at said crucibles; articles to be coated placed on a holder internally within said vacuum chamber; a plurality of tubes protruding into said vacuum chamber supplying oxygen gas to said articles; whereby upon actuation of said electron beam guns and release of said oxygen gas, primary ceramic and secondary ceramic or oxidized metallic vapor clouds are produced from said crucibles coating said articles with a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous, nanometer—to micron-sized layers of ceramic material which have dispersed oxide particles (molecules) of secondary ceramic or oxidized metallic material, with a multiphase interfacial layer, consisting of finely dispersed nanometer-sized particles of secondary ceramic or oxidized metallic material, primary ceramic material, and nanometer-sized porosity separating each layer of primary ceramic material.
 20. The apparatus of claim 19, wherein said primary ceramic material is a stabilized zirconia ingot and said metallic material is an aluminum or tantalium ingot.
 21. The apparatus of claim 19, wherein power from said electron beams is apportioned to the crucibles such that the majority of said vapor cloud that deposits onto said article will be derived from said primary crucible and the balance of the vapor cloud that deposits onto said article will be derived from said secondary crucible.
 22. The apparatus of claim 19, wherein power from said electron beam gun directed at said secondary crucible is periodically pulsed to change the evaporation rate to a fraction of the rate of evaporation of said primary crucible, and to enable deposition of a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous layers.
 23. The apparatus of claim 19, wherein the rates of coating deposition and article rotation are controlled such that the multilayer zone within the thermal barrier coating may have a minimum of one interfacial layer per micron of coating thickness.
 24. The apparatus of claim 19, wherein evaporation from said secondary crucible is pulsed.
 25. The apparatus of claim 19, wherein one electron beam gun protrudes into said vacuum chamber, and the electron beam emitted from said electron beam gun jumps between said primary and secondary crucible to achieve continuous rates of evaporation.
 26. The apparatus of claim 19, wherein the gas traversing through said tubes contains an inert gas such as argon.
 27. The apparatus of claim 19, wherein RF ion generators are utilized to generate RF ion electrical fields to ionize said ceramic and metallic vapor clouds.
 28. The apparatus of claim 19, wherein said articles are positioned and moved from a stabilized zirconia vapor cloud to a secondary vapor cloud depositing a concentration of the alumina or tantalum oxide vapor.
 29. A coating deposition apparatus comprising, a vacuum chamber; a primary crucible and a secondary crucible placed internally within said vacuum chamber; a primary ceramic or metallic material placed internally within said primary crucible; a secondary ceramic or metallic material placed internally within said secondary crucible; one or more electron beam guns inside said vacuum chamber; electron beams aimed toward the upper surface of the materials within said primary and secondary crucibles; articles to be coated placed on a holder within said vacuum chamber; electrical and/or other heat sources that maintain articles within a temperature range during deposition of the coating; one or more gas bleed supply tubes protruding into said vacuum chamber; gas, traversing through said oxygen bleed supply tubes, aimed in the direction of said articles; whereby upon actuation of said electron beam guns and release of said gas, vapor clouds are produced from said materials within the primary and secondary crucibles which coat said articles with a multilayer coating composed of an alternating sequence of non-homogeneous, nanometer—to micron-sized layers of primary material which have dispersed particles (molecules) of secondary material, with a non-homogeneous nanometer—to micron-sized layer of secondary material (which have dispersed particles of primary phase) or a multiphase interfacial layer (consisting of finely dispersed nanometer-size particles of secondary material, the primary material, and nanometer-size porosity) separating each.
 30. A method of depositing a thermal barrier coating on articles, comprising the steps of: positioning one or more articles, such as turbine blades or vanes, within the mixing zone of a primary ceramic vapor cloud and a secondary ceramic or oxidized metallic vapor cloud produced by separate deposition sources; simultaneously heating and melting a portion of each of the ceramic and metallic materials to produce a primary ceramic vapor cloud and a secondary ceramic or oxidized metallic vapor cloud that coexist within a vacuum chamber; adding oxygen to said vacuum chamber through oxygen bleed supply tubes to convert metallic vapor to an oxide vapor and directing it toward the articles to be coated which are placed on a rotating holder; apportioning power from an electron beam to the primary and secondary sources, whereby at least 85% of the vapor that deposits onto said articles will be derived from the ceramic source and at least 1% will be derived from the metallic source; rotating the articles within the combined vapor clouds such that the mixed vapors may deposit a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous layers, the layers being composed of the primary ceramic material having dispersed oxide particles (molecules) of the second material and a multiphase interfacial layer separating each of the primary material layers; controlling the rates of coating deposition and article rotation rates such that the multilayer zone within the thermal barrier coating has a minimum of one interfacial layer per micron of coating thickness.
 31. The method of claim 30, wherein the primary ceramic material is stabilized zirconia and the secondary ceramic or metallic material is predominately Al₂O₃, Al, Ta₂O₃, or Ta.
 32. The method of claim 30, wherein the interfacial layers consist of a mixture of finely dispersed particles of secondary ceramic or oxidized metallic material and primary ceramic material.
 33. A method of depositing a thermal barrier coating on articles, comprising the steps of: positioning one or more articles within the mixing zone of the primary ceramic vapor cloud and the secondary ceramic or oxidized metallic vapor cloud produced by separate deposition sources comprised of stabilized zirconia and Al₂O₃, Al, Ta₂O₅ or Ta; simultaneously heating and melting a portion of each of said primary ceramic and secondary ceramic or metallic materials to produce a ceramic and an oxidized metallic vapor cloud that coexist within a vacuum chamber, adding oxygen gas to the chamber to convert any metallic vapor to an oxide vapor and directing it toward the articles to be coated which are placed on a non-rotating holder; apportioning power from electron beams to the primary ceramic and secondary ceramic or metallic sources such that the majority of the vapor that deposits onto the articles is derived from the ceramic source and the balance is derived from the metallic source; pulsing power to the secondary ceramic or metallic source to enable deposition of a multilayer thermal barrier coating composed of an alternating sequence of non-homogeneous layers composed of the primary ceramic material which may have dispersed oxide particles of the secondary ceramic or oxidized metallic material and a multiphase interfacial layer separating each of the primary ceramic layers; controlling the rates of pulsed deposition from the metallic source such that the multilayer zone within the thermal barrier coating has a minimum of one interfacial layer per micron of coating thickness; periodically increasing and decreasing the power to the electron beams so that pulsed evaporation from the secondary ceramic or metallic evaporation source is also achieved by changing the raster pattern of a focused electron beam from a large area to a small area.
 34. The method of claim 33, wherein pulsed evaporation rate from the secondary ceramic or metallic source is achieved by changing the power density of the electron beam from a large beam (low power density) to a focused beam (high power density).
 35. The method of claim 33, wherein said article has been previously coated with a bond coat.
 36. The method of claim 33, wherein vapor from said alumina ingot is used to deposit a less than 5 micron dense alpha alumina layer onto said article prior to starting deposition of the multilayer thermal barrier coating.
 37. The method of claim 33, wherein said article's substrate is a nickel-base superalloy.
 38. The method of claim 33, wherein said article's substrate is silicon nitride.
 39. The method of claim 33, wherein said article's substrate is a SiC_(fiber)/SiC_(matrix) composite.
 40. The method of claim 39, wherein said article's substrate is a Si melt infiltrated. 